Silver-Catalyzed C(sp³)-H Functionalization

Silver catalysis has emerged as a versatile tool for C-(sp³)-H bond functionalization, offering unique opportunities to transform simple hydrocarbons into valuable products. Both activated and unactivated C-(sp³)-H bonds have been investigated in recent years. However, most studies have focused on activated bonds. In these protocols, in situ generation of nitrene intermediates has dominated the field, enabling efficient and selective C-(sp³)-H bond transformations. These reports demonstrate that ligand design, in addition to the nature of the silver catalyst, plays a crucial role in achieving chemo-, site-, and even stereoselectivity. During the past decade, silver-catalyzed functionalization has been used for the conversion of C-(sp³)-H bonds into C-C, C-N, C-O, and C-X (X = halogen) bonds. These protocols have shown that Ag-(I) combined with suitable oxidants can be used as a powerful synthetic tool for the functionalization of specific C-(sp³)-H bonds into desired C-Z bonds. This review highlights the advances and limitations in silver-catalyzed C-(sp³)-H functionalization that have been reported during the past decade.